CN1419592A - Laminar articles containing layer of ethylene containing polymer elastomers containing aromatic resins - Google Patents

Laminar articles containing layer of ethylene containing polymer elastomers containing aromatic resins Download PDF

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Publication number
CN1419592A
CN1419592A CN01803679A CN01803679A CN1419592A CN 1419592 A CN1419592 A CN 1419592A CN 01803679 A CN01803679 A CN 01803679A CN 01803679 A CN01803679 A CN 01803679A CN 1419592 A CN1419592 A CN 1419592A
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CN
China
Prior art keywords
goods
rubber
resin
diene
norbornene
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Pending
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CN01803679A
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Chinese (zh)
Inventor
K·卢塔斯
V·B·加勒兹
E·P·乔丹
T·J·雷诺尔兹
G·斯特拉
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Priority claimed from GBGB0000674.2A external-priority patent/GB0000674D0/en
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of CN1419592A publication Critical patent/CN1419592A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Multilayer articles such as V-belts, hoses, rubber sheets, tires are produced from ethylene, alpha-olefin, or ethylene, alpha olefin diene copolymer elastomers which despite their attractive properties, have not been used previously due to the lack of green tack. The problem of insufficient green tack is overcome by the incorporating an aromatic containing petroleum resin.

Description

The laminated product that comprises the layer of ethylene containing polymer elastomers that contains resin
Invention field
The present invention relates to laminated product, it comprises the elastic composition with improved rubber viscosity, makes it possible to vulcanize and does not need tackiness agent thereby particularly have integrally-built elastic composition that enough viscosity has a sufficient intensity with formation.But rubber viscosity is used to refer to the binding property of vulcanized rubber products before sulfuration.
Background of invention
Natural and synthetic rubber and elastomerics are widely used in produces for example V-belt of multi-layer product, and flexible pipe is used for the thin slice of roof, mat and tire.The example of institute's materials used is a chloroprene, natural and synthetic rubber, for example chloroprene rubber, isoprene-isobutylene rubber, styrene butadiene ribber and elastoprene.Typical rubber composite is by calendering and mixes and produce, so that for example additives such as filler, pigment, oxidation inhibitor and vulcanizing agent can thoroughly be scattered in the whole rubber.In case mixture forms, just can be, shelve, vulcanize or produce end article by coextrusion and sulfuration subsequently by form layers.The V-strapped process of typical production comprises the lamination bar of making carrying material, and normally layer structure vulcanized bar then along assembly drum.Therefore, the layer of laminar structure has enough rubber viscosity and comes bonded to each other and the two ends of band are tightly sticked together, and this point is very important.
Rubber can be used for producing tire similarly.Tire is the aggregate of different rubber layer, and each layer all plays specific function, strengthens and is installed on the circle by fabric and/or cable wire.In tire production, rubber layer is laminated to that other layer of tire is gone up and tyre vulcanization forms one-piece construction.Equally, rubber layer has enough rubber viscosity with bonding with other layer before sulfuration, and this point is important.
Flexible pipe is the typical multi-layer product of producing by coextrusion and sulfuration subsequently.Usually, between the sulfuration of coextrusion and autoclave arranged one period shelf lives, to keep one-piece construction be very important to rubber viscosity when storing.
Chloroprene is in being usually used in these goods, because the enough binding propertys before the sulfuration have been introduced in the existence of chlorine.Yet from the viewpoint of environment, and because it has caused the loss of properties on aging of rubber, the existence of chlorine is unfavorable.When using other elastomerics, use tackiness agent that component is kept together before sulfuration, for example, in European patent 195273.It is expensive using tackiness agent, needs other step aborning and may cause having weak link in finished product destruction and the finished product.
Ethylene copolymer or terpolymer elastomerics are because they have barrier, elasticity and elastic combination, so be to be used for for example attractive material of V-belt, flexible pipe, mat and tire of article of manufacture, because its good ozone resistants makes them particularly useful in the production of tire.Yet, do not make them can be before sulfuration and the enough bonding one-piece constructions that produces of other layer formation because they do not have enough rubber viscosity, so they are not used.
Propose among the european patent application 0685511A, the hydrogenant petroleum resin can be introduced in the hydrocarbon rubbers, for example ethene, propylene copolymer rubbers, the propylene diene copolymer rubber, natural rubber, synthetic polyisoprene, styrene-butadiene-copolymer rubber and divinyl rubber are so that improve processibility.This rubber it is said that binding property is not enough, and viscosity is too high, wraps roller in the course of processing, and the viscosity of vulcanized rubber is bad.EP 0685511 begins to overcome this problem, although promptly tackifier can improve processing characteristics, influences the physicals and the thermotolerance of vulcanized rubber unfriendly, it is said that this problem can solve by using hydrogenated petroleum resin.
Therefore, EP 0685511 does not relate to rubber viscosity and relates to the processibility of rubber and the performance of vulcanized rubber.Otherwise, the present invention relates to improve the rubber viscosity of ethene, alpha-olefin copolymer rubber and ethene, alpha-olefin, diene copolymers rubber.Particularly ethylene propylene copolymer rubber and ethene, propylene, diene copolymers rubber.
Summary of the invention
Yet, we have found that ethene, alpha-olefin copolymer rubber or the ethene, alpha-olefin, the diene elastomer terpolymer layer that contain aromatic hydrocarbon resin have enough rubber viscosity, make it possible to form one-piece construction, be used for sulfuration subsequently and do not need other tackiness agent with sufficient intensity.
Therefore, the invention provides a kind of multilayered structure, wherein comprise one deck at least, the blend that this layer contains ethene, alpha-olefin copolymer and/or ethene, alpha-olefin, diene elastomer terpolymer and contain the hydrocarbon resin of aromatics.
The invention further relates to the hydrocarbon resin that contains aromatics and be used to improve the purposes of the rubber viscosity of ethene, alpha-olefin copolymer rubber and/or ethene, alpha-olefin, diene terpolymer rubber.
The present invention further provides a kind of production method of rubber composite, this rubber composite comprises ethene, alpha-olefin copolymer rubber and/or ethene, alpha-olefin, the diene terpolymer rubber that contains aromatic hydrocarbon resin, wherein rubber is at first compound with other additive, adds aromatic hydrocarbon resin in the back half-life of compounding period.
The present invention further provides a kind of method of producing multi-layer product, comprise that preparation contains the layer of ethene, alpha-olefin copolymer rubber and/or ethene, alpha-olefin, diene copolymers rubber and aromatic hydrocarbons petroleum resin, and this is placed on the second layer, randomly vulcanizes this composite structure. Detailed Description Of The Invention
The elastomer polymer that comprises ethene that the present invention uses is and one or more more high-grade alpha olefin monomers and the polymkeric substance that randomly obtains with the diene monomers copolymerization.When being applied to these polymkeric substance, term " elastic " or " elastomerics " are defined as when they are crosslinked, can be replied fast and forcefully by gross distortion.When not adding thinner, crosslinked polymkeric substance discharges after being stretched to double length and keeping one minute at 18 ℃ to 29 ℃, can be retracted to 1.5 times less than former length in one minute.
The elastomer polymer that comprises ethene also comprises one or more more high-grade monoolefines, particularly has the alpha-olefin of 3 to 25 carbon atoms.The more high-grade monoolefine that is suitable for using can be side chain or straight chain, ring-type and aromatics, replacement or unsubstituted, preferably have the alpha-olefin of 3 to 16 carbon atoms.The example of the indefiniteness of preferred alpha-olefin is propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene and 1-laurylene.Also can use blended alkene (for example propylene and 1-butylene, mixed butene or the like).
Alpha-olefin is introduced the elastomer polymer that comprises ethene with about amount of 15 to about 85wt% usually, and more preferably about 15 to about 70wt%, particularly preferably is about 20 to about 60wt%.
The alpha-olefin that this class replaces for example is formula H 2C=CH-C nH 2nCompound shown in the-X ', wherein n is 1 to 20 integer (preferred 1 to 10), and X ' comprises aryl, alkaryl or cycloalkyl.Can also be by the alpha-olefin of one or more these X ' substituting groups replacements, wherein substituting group is bonded on the non-terminal carbon, and condition is that substituted carbon atom is not the 1-or the 2-carbon potential of alkene.In two rings that alkyl replaces and the alpha-olefin of bridging are also included within, preferred C 1-C 9The norbornylene that alkyl replaces (for example 5-methyl-2-norbornylene, 5-ethyl-2-norbornylene, 5-(2 '-ethylhexyl)-2-norbornylene, vinyl norbornene or the like).
Being suitable for preparing the used non-conjugated diene that contains the polymkeric substance of diene of the present invention can be to have the straight chain hydrocarbon diolefine of 6 to 15 carbon atoms or the alkene that cycloalkenyl group replaces.In the middle of, preferred diene is a Dicyclopentadiene (DCPD), 1,4-hexadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene.Particularly preferred diene is 5-ethylidene-2-norbornene and 1, the 4-hexadiene.Obviously, also can use the mixture of these diene.In containing the elastomer polymer of ethene, the content of optional diene monomers can be 0.5 to 15wt%, and if you are using, preferred 0.5 to 12wt%, and most preferably 1.0 to about 6.0wt%.
The molecular weight that contains the polymkeric substance of ethene is measured with NMR, and weight-average molecular weight (Mw) typically is 5000 to 5000000, more typically is 10000 to 500000Mw, typically is 15000 most to 350000Mw.Mooney viscosity (ML 1+4, 125 ℃) and be generally 10 to 90, be more typically 20 to 75.
This elastomerics can prepare in the polymerization reactor of routine, can carry out polyreaction under the Z-type catalyst temperature of (comprising traditional Ziegler-Natta catalyst and newer 3-10 group 4 transition metal single-point catalyst (homologue of metallocenes, diimino and diamido structure or the like)) any being suitable for, for example approximately-100 ℃ to about 150 ℃ temperature, or 10 ℃ to about 100 ℃ of preferably approximatelies, more preferably about 0 ℃ to about 60 ℃.The used pressure of polymerization technique can change to the scope of about 600Kpa at about OKpa.Perhaps metalloscene catalyst can be used to prepare elastomerics, for example is described among open WO99/45047 of US patent 5837787,5625016,5696213 and PCT and the WO99/45049, and all documents are incorporated herein by reference herein.
Can make effective any known thinner of reaction mixture or solvent can be used to carry out polymerization.For example Shi Yi thinner or solvent are varsols, as aliphatics, cyclic aliphatic and aromatic hydrocarbons solvent, or the halides of these solvents.
In addition, known adding " branching inhibitor " is to reduce the degree of branching.Known by prior art, some Lewis base such as NH 3It is effective branching inhibitor.In addition, have been found that in recent years some organoalkoxysilane is (as methyl silicate (Si (OMe) 4), tetraethyl silicate (Si (OEt) 4) etc.) play a part effective branching inhibitor, and can not reduce catalyst efficiency or reactive behavior.Thereby catalyst system of the present invention can be used for any known solution polymerization process.
After the polymerization, make the polymerization reaction mixture chilling with currently known methods at reactor exit.Can finish this quench step as quench liquid by in polymerization reaction mixture (for example polymerisate discharging current), adding entry, lower alcohol or aqueous acids (for example hydrochloric acid soln).
A kind of method that is used for preparing Resilient product is described in US patent 4540753.In the middle of point out, in a kind of " no mixing reactor ", carry out this method, wherein between the reaction mixture each several part, do not mix basically, this reaction mixture is included in the polymer chain that different time causes.This typical tubular reactor polymerization process makes does not have " back-mixing " and basic in the axial direction not mixing basically.Another preferred manufacture method and preferred elastomerics are described among the european patent application 0227206A, are incorporated herein by reference herein.
The polymerization of the petroleum stream by comprising monomer mixture can obtain can be used for the hydrocarbon resin that contains aromatics of blend of the present invention.As selection, also can prepare them by the polymerization of pure aromatic monomer.In order to make blend of the present invention obtain desirable aromatic content, can also obtain these resins by the blend of resin (for example contain the resin of aromatics and do not contain the resin of aromatics, perhaps contain two kinds of resins of different amount aromatics).
Typical feedstream comprises the monomer of 20wt% to 80wt% and the solvent of 80wt% to 20wt%.Preferably, feedstream comprises the monomer of 30wt% to 70wt% and the solvent of 70wt% to 30wt%.More preferably, feedstream comprises the monomer of about 50wt% to 70wt% and the solvent of 50wt% to 30wt%.Solvent can comprise aromatic solvent.Aromatic solvent can comprise at least a in toluene, dimethylbenzene and the aromatic petroleum solvent.Solvent also can comprise aliphatic solvents.Solvent can be not polymerisable component in the logistics.
Usually, aliphatic feed comprises C at least 5Monomer by heating under 100 ℃ to 160 ℃ temperature and distillation classification, can be removed cyclopentadiene and methyl cyclopentadiene component from feedstream.C 5Monomer can comprise at least a following monomer that is selected from: divinyl, iso-butylene, 2-methyl-2-butene, 1-amylene, 2-Methyl-1-pentene, 2-methyl-2-amylene, 2-amylene, cyclopentenes, tetrahydrobenzene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene and Dicyclopentadiene (DCPD).Feedstream can comprise C at least 5Monomer, wherein feedstream comprises the polymerisable monomer of 70wt% at least, this polymerisable monomer contains the 1,3-pentadiene of 50wt% approximately at least.Feedstream also can comprise the isoprene of low levels, contains some 2-methyl-2-butene usually, and can comprise one or more cyclodiene.
Feedstream may further include the chain-transfer agent up to 40wt%, preferably up to the chain-transfer agent of 20wt%.Chain-transfer agent can comprise at least a following material: the C that is selected from 4Alkene, C 5Alkene, C 4The dimer of alkene and C 5The dimer of alkene.Chain-transfer agent can comprise at least a following material that is selected from: iso-butylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, its dimer and oligopolymer thereof.
On the other hand, feedstream comprises the C of 30wt% to 95wt% 5Monomer and 70wt%'s to 5wt% is co-fed, and this is co-fed to comprise at least a pure monomer, the C of being selected from 9Monomer and terpenic material.Preferably, feedstream comprises the C of 50wt% to 85wt% 5Monomer and 50wt%'s to 15wt% is co-fed, and this is co-fed to comprise at least a pure monomer, the C of being selected from 9Monomer and terpenic material.Pure monomer is preferably the aromatic hydrocarbon monomer, for example vinylbenzene, alpha-methyl styrene or Vinyl toluene.
If feedstream comprises C at least 9Aromatic monomer, then C 9Monomer can comprise at least a following monomer that is selected from: vinylbenzene, Vinyl toluene, indenes, Dicyclopentadiene (DCPD) and alkylating derivative thereof.C 9Monomer can contain the polymerisable unsaturated hydrocarbons of 20wt% at least.C 9Monomer can comprise the polymerisable unsaturated hydrocarbons of 30wt% to 75wt%.C 9Monomer can comprise the polymerisable unsaturated hydrocarbons of 35wt% to 70wt%.
The pure monomer feedstream can contain purer styrene-based monomers, for example vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, 4-vinyl toluene and Vinyl toluene fraction.These monomers can be used as pure component or use as the mixture of two or more monomer feed, so that obtain desirable resin property.Preferred mixture comprises the alpha-methyl styrene of 20wt% to 90wt% and one or more comonomers of 80wt% to 10wt%, the mixture of optimization styrene, Vinyl toluene, 4-vinyl toluene or these components.In addition, other alkylated styrenes also can be used as monomer of the present invention, for example t-butyl styrene or styryl phenyl.
In yet another aspect, feedstream comprises the C of 30wt% to 95wt% 9Monomer and 70wt%'s to 5wt% is co-fed, and this is co-fed to comprise at least a pure monomer, the C of being selected from 5Monomer and terpenic material.Preferably, feedstream comprises the C of 50wt% to 85wt% 9Monomer and 50wt%'s to 15wt% is co-fed, and this is co-fed to comprise at least a pure monomer, the C of being selected from 5Monomer and terpenic material.
Carry out polymerization in a continuous manner or with intermittent mode.Can catalyzed reaction, thermocatalysis or acid catalyzed reaction; Particularly preferred catalytic way is not described in and examines in the UK Patent Application 9916858,9916849 and 9916855, is incorporated herein by reference herein.The reaction times of intermittent mode was generally 30 minutes to 8 hours, and preferred 1 hour to 4 hours, temperature of reaction was-50 ℃ to 150 ℃, and preferred-20 ℃ to 100 ℃, more preferably 0 ℃ to 70 ℃.Can stop polymerization by from hydrocarbon resin, removing catalyzer.Can from hydrocarbon resin, remove catalyzer by filtering.Can in the mixed bed reactor that contains catalyzer, remove hydrocarbon resin, and can the strip, hydrocarbons resin and remove unreacted monomer, solvent and low-molecular-weight oligomer.Unreacted monomer, solvent and low-molecular-weight oligomer can use in recirculation.
About C 5Raw material monomer stream, except reactive component, the not polymerizable components in the charging can also comprise stable hydrocarbon, this stable hydrocarbon can with unsaturated component condistillation, this stable hydrocarbon for example is pentane, pentamethylene or 2-methylpentane.This monomer feed can with the C as chain-transfer agent 4Or C 5Alkene or dimer copolymerization.Can add chain-transfer agent, have lower and the resin of narrow molecular weight distributions more with the resin that obtains to make than only using monomer.Chain-transfer agent seals the end of the chain in the mode that the polymkeric substance of regenerating causes point, thereby stops the growth of the polymer chain of growth.The component that plays the chain-transfer agent effect in these reactions includes but not limited to iso-butylene, 2-methyl-1-butene alkene, 2-methyl-2-butene or their dimer or their oligopolymer.Can add chain-transfer agent in reaction with the form of pure substance or with the form of solvent cut, perhaps chain-transfer agent is a component of charging.
Preferred polymer solvent is an aromatic solvent.Typical case's representative is toluene, dimethylbenzene or light aromatic petroleum solvent.These solvents can use fresh or recycle from processing.Solvent generally comprises the water less than 200ppm, preferably less than the water of 100ppm, most preferably less than the water of 50ppm.For C 5And/or C 9Polymerization, preferred solvent is an aromatic solvent.Usually, unreacted sylvic oil component is recycled in technology as solvent.Except the solvent of recirculation, also can use toluene, dimethylbenzene or aromatic petroleum solvent.These solvents can use fresh or recycle from processing.Solvent generally comprises the water less than 500ppm, preferably less than the water of 200ppm, most preferably less than the water of 50ppm.Solvent can also be not polymerisable component in the charging.
About polymeric reaction condition, the first important variable is the amount of catalyst system therefor.Based on monomeric weight meter, preferably use the catalyzer of 0.1wt% to 30wt%.For pure monomer resin, concentration is preferably 0.1 to 15wt%, more preferably 0.5wt% to 10wt%, and 0.5wt% to 8wt% most preferably.For C 5Monomer, concentration are preferably 0.5 to 30wt%, more preferably 1wt% to 20wt%, and 3wt% to 15wt% most preferably.For C 9Monomer, concentration are preferably 0.5 to 30wt%, more preferably 1wt% to 20wt%, and 3wt% to 15wt% most preferably.
The selection of ethene, alpha-olefin copolymer or ethene, alpha-olefin, diene elastomer and hydrocarbon resin will be depended on specific laminate structure.Similarly, the amount that should add the resin in the blend will depend on the structure of being envisioned.The end-use of many anticipations is used 1 to 25% resin, more preferably 3 to 25% resin.Especially, 4 to 15% resin can bring the elastomeric binding property of required degree.Particularly in the elastomerics 4 to 15%, preferred 5 to 12% resin can provide a kind of V-strapped composition that is particularly useful for producing.
The aromatic content of preferred resin also depends on structure.Aromatic content calculates according to the vinylbenzene equivalent, and what recorded by nuclear magnetic resonance spectrum is 3% to 75%, and is preferred 4% to 50%, and more preferably 5% to 20%, so that the rubber viscosity of enough ethylene elastomer is provided.
After preparing resin, can make it color and improve colour stability to subtract light color subsequently through over hydrogenation.The hydrogenation of resin is that prior art is known.Can use any known method that is used for the catalytic hydrogenation of hydrocarbon resin, particularly suitable is the method for US 5171793, US 4629766, US5502104 and US 4328090 and WO95/12623.General hydrogen treatment condition is included in the reaction to the hydrogen pressure of 300 normal atmosphere (30390kPa) of about 100 ℃-350 ℃ and 5 normal atmosphere (506kPa), for example 10 to 275 normal atmosphere (1013kPa to 27579kPa).In a specific embodiments, temperature range is 180 ℃ to 320 ℃, and pressure range is the hydrogen of 15195kPa to 20260kPa.(25 ℃, 1 normal atmosphere (101kPa)) send into hydrogen in the reactor and the volume ratio of charging generally is 20-200 under standard conditions; For the preferred 100-200 of water-white resin.
Another is applicable to that resin hydrogenant method of the present invention is described among the EP 0082726.EP 0082726 discloses a kind of catalytic hydrogenation or hot hydrogenant method that is used for petroleum resin, adopts the nickel-tungsten catalyst that is stated from the gamma-aluminium oxide carrier, and wherein hydrogen pressure is 1.47 * 10 7-1.96 * 10 7Pa, temperature is 250-330 ℃.Generally at 160 ℃ to 320 ℃ and 9.8 * 10 5To 11.7 * 10 5Carry out hot hydrogenation under the pressure of Pa, carried out usually 1.5 to 4 hours.After the hydrogenation, the mixture in the flushing reactor further separates this mixture to reclaim the hydrogenant resin.Can adopt steam distillation to remove oligopolymer, preferably be no more than 325 ℃ of resin temperatures.
In a preferred specific embodiments, by being contacted, resin carries out hydrogenation in the presence of hydrogen and hydrogenation catalyst metallic compound, and this metallic compound is carried on the fire-resistant substrate particles of porous, and the fire-resistant substrate particles of this porous has:
A) average maximum diffusion path length is less than or equal to the twice of hydraulic radius
B) pore volume distribution:
I) the shared volume in hole of diameter＞150000 is greater than about 2% of cumulative volume
Ii) diameter＞20000 and＜the shared volume in hole of 150000 greater than cumulative volume about 1% and
Iii) diameter＞2000 and＜the shared volume in hole of 20000 is about 12% greater than cumulative volume, and
C) total pore volume accounts for 45% to 86% of substrate particles cumulative volume.
In particularly preferred specific embodiments, catalyzer comprises nickel and/or the cobalt that is stated from one or more molybdenums, tungsten, aluminum oxide or the silica supports.In a preferred specific embodiments, the nickel oxide on the carrier and/or the amount of cobalt oxide are 2 to 10wt%.After preparation, the Tungsten oxide 99.999 on the carrier or the amount of molybdenum oxide are 5 to 25wt%.Preferably, catalyzer comprises 4 to 7wt% nickel oxide and 18 to 22wt% Tungsten oxide 99.999.This method and suitable catalyzer all are described in greater detail in the US patent 5820749.
In another preferred specific embodiments, can adopt US patent 4629766 described methods and catalyzer to carry out hydrogenation.Especially preferably be stated from the nickel-tungsten catalyst on the gama-alumina.
Elastomerics and resin can mix in any suitable manner, for example admixture of powder, extraction blend, calendering and granulation, and can be used as preformed blend and offer manufacturers.If in calendering or back half-life of mixing period resin is joined in the elastomerics then can obtain excellent rubber viscosity.
The used layer of the present invention can also comprise other resins, and for example derived from the rosin ester class of Yatall MA, gum resin and polyterpene, it can add during composition operation.
Except ethylene copolymer and terpolymer and hydrocarbon resin of the present invention, multi-layer product of the present invention also will comprise any natural and synthetic rubber in the known laminated product that contains ethylene elastomer that is usually used in having prior art.Example comprises natural rubber, chloroprene, chloroprene rubber, isoprene-isobutylene rubber, styrene butadiene ribber, isoprene, divinyl rubber and other polydiene rubbers.
Following other additives can be joined in the rubber composite.
Vulcanizing agent and/or linking agent.Here use the chemical reagent that is usually used in cross-linked elastomer, for example various forms of Sulfurs, as pulverized sulfur, precipitated sulfur, sulfoid, surface-treated Sulfur and insoluble sulfuy, sulphur compound such as sulfur subchloride, sulfur dichloride, morpholine disulphide and alkyl phenol disulfide; Inorganic sulphide agent outside the sulphur removal, for example selenium and tellurium; And para-quinone dioxime (p-quinonedioximer), right, to the dibenzoyl quininie dioxime (p, p-dibenzolyquinonedioxine), tetrachloro-right-benzoquinones and poly--paradinitrobenzene.
As selection, organo-peroxide also can be used for crosslinked.The example of suitable superoxide comprises tertbutyl peroxide; 1; 1; 3; 3-tetramethyl--butylhydroperoxide; p-methane hydroperoxide; cumene hydroperoxide; the hydroperoxidation diisopropyl benzene; 2; 5-dimethylhexane-2; the 5-dihydro-peroxidase; di-t-butyl peroxide; dicumyl peroxide; the tert-butyl peroxide cumyl; 1; two (tert-butyl peroxide) cyclododecanes of 1-; 2; two (tert-butyl peroxide) octanes of 2-; 1; the 1-cyclohexane di-tert-butyl peroxide; 2; 5-dimethyl-2; 5-two (tert-butyl peroxide) hexane; 2; 5-dimethyl-2; 5-(tert-butyl peroxide)-3-hexin; 1; two (tert-butyl hydroperoxide sec.-propyl) benzene of 3-; 2; 5-dimethyl-2; 5-(benzoyl peroxide base) hexane; 1; two (tert-butyl peroxide)-3 of 1-; 3; the 5-trimethyl-cyclohexane; normal-butyl-4; two (tert-butyl peroxide) valerates of 4-; benzoyl peroxide; toluene between peroxidation; chloro benzoyl peroxide; 2,4 dichlorobenzoyl peroxide; the tert-butyl hydroperoxide isobutyrate; tert-butyl hydroperoxide-2-ethyl-hwxanoate; tert butyl peroxy benzoate; tert-butyl hydroperoxide sec.-propyl carbonic ether and tert-butyl hydroperoxide allyl carbonate.
Other additives comprise vulcanization accelerator, for example guanidine class, aldehyde-amine, aldehyde-Ammonia, thiazoles, sulfamido, Thiourea, thiurams, dithiocarbonic acid salt, xanthate class, phosphorodithioic acid salt and dithio acid esters material.Their uses of can using separately or be bonded to each other.Enhancer activator, for example metal oxide, metal carbonate, lipid acid and derivative thereof and amine; Also have scorch retarder, for example organic acid, nitroso compound, sulfo-phthalic imidine and sulphone amide derivative.
In addition, additive can comprise anti-aging agent, oxidation inhibitor and antiozonant, for example naphthylamines class, phenylbenzene amine, P-pHENYLENE dI AMINE class, quinoline, hydroquinone derivatives, monobasic phenols, dihydric phenols, ternary phenols, polyatomic phenol, thiobis phenols, Hinered phenols, phosphorous acid esters, thio-2 acid salt, benzimidazoles, dithiocarbonic acid nickel class, Thiourea, triazole species and these materials of wax; And UV absorption agent and photostabilizer, for example salicyclic acid derivatives, benzophenone, benzotriazole category, N, N '-phenylbenzene oxalamide derivative, hydroxy-benzoic acid salt and these materials of hindered amines.They can be used alone or in conjunction with each other.
Additive can further comprise tenderizer, for example petroleum lubricant (process oil), ethylene ' alpha '-olefin oligopolymer, paraffin, whiteruss, white oil, Vaseline, oil, sultanate, stellar coal, pitch, diene oligomer (comprising its hydride), vegetables oil tenderizer (Viscotrol C, Oleum Gossypii semen, rapeseed oil, plam oil, peanut oil, pine tar, Yatall MA etc.), rubber substituent (vulcanized oil), lipid acid, soap and fatty acid ester.Their uses of can using separately or be bonded to each other.
Further, additive comprises strongthener and filler, for example carbon black (thermally oxidized black, furnace treated black, thermal black or dim, acetylene black etc.), silicon-dioxide (white carbon black etc.), alkaline magnesium carbonate, lime carbonate (as light calcium carbonate, grinding calcium carbonate and surface-treated lime carbonate), Magnesium Silicate q-agent (as ultra-fine Magnesium Silicate q-agent), clay, talcum, wollastonite, zeolite, diatomite, silica sand, alumina sol, aluminium hydroxide, Tai-Ace S 150, barium sulfate, calcium sulfate, lithopone, molybdenumdisulphide, rubber powder, shellac, dust cork and cellulose powder.Adhesion promotor for example zinc methacrylate is also includable, used cord during rubber layer sticks to other materials for example V-belt is made if desired.The use of can using separately or be bonded to each other of these additives.
At last, additive comprises other additive, comprises peptizing agent, whipping agent, frothing aid, slip agents, inner pattern releasing agent applicable, antifogging agent, fire retardant, inner static inhibitor, tinting material (pigment and dyestuff), coupling agent, antiseptic-germicide, mould inhibitor and reodorant.
Rubber combination is in case formation just can change it into layer by some technology.For example, its calendering can be become thin slice or be extruded as long goods such as flexible pipe.
In V-strapped production, at first make rubber and little fiber composite, then form layers on stack.Thereby the layer that then cord is dispersed in these fiber filled is gone up and is formed sheet material.Afterwards this sheet material is cut into strips; With domain of each bar coiled, terminal continuous then, and make this system sulfuration.Therefore have been found that resin is added in the elastomerics and can bring enough rubber viscosity to elastomerics,, can vulcanize and need not other tackiness agent so that itself and other layer formation has the bonding of sufficient intensity.
In the production of tire, comprise resin in the elastomerics, can provide enough rubber viscosity to elastomerics, make that it can be as the side-wall material of tire.Bringing elastomeric binding property makes it possible to produce and has enough fusible layer, it will stick on other side-wall material, for example natural rubber, chloroprene, isoprene-isobutylene rubber and styrene/butadiene rubbers make it possible to form one-piece construction before sulfuration.By this way, can form one deck, the especially side wall layer of tire by ethene, alpha-olefin diene elastomer, thereby produce improved ozone proof performance.
In the production of flexible pipe, general each layer of coextrusion cuts the coextrusion thing to desirable length, vulcanizes in autoclave subsequently.Adopt the inventive method, the layer of coextrusion has enough rubber viscosity, can store before sulfuration and can not damage the coextrusion thing.
With further explanation the present invention, wherein use following product by following embodiment:
A kind of sooty ethylene/propylene/diene elastomerics that contains
A kind of standard V-belt composition based on chloroprene rubber
Escorez?5600 TM
Escorez 2520 TM, the two is all from ExxonMobil Chemical Company, Houston, and TX buys
Adopt Monsanto Tel-Tak machine to measure Tel-Tak, Tel-Tak separates two coarctate identical required power of test bars.Following this process of carrying out:
-at first make rubber compressing tablet in mill, being prepared into 0.15 to 0.20cm thick thin slice,
-rubber sheet is placed on a slice Mylar (polyester film), the composite surface that makes contact mill roll down (Mylar thickness: 0.1-0.2mm), note avoiding retaining any bubble between compound foil and the Mylar film,
The bonding pressure roller of-employing is pressed in Mylar downwards tightly with mixture and goes up and make it cooling,
-the Mylar side form from compound foil downcuts batten then.
The lower clamp of Monsanto Tel-Tak device is moved to lower end position, and desirable weight is placed on the counterweight support.Available weight is:
Anchor clamps: 8 ounces (± 226.6g)
Anchor clamps+8 ounce: 16 ounces (± 453.2g)
Anchor clamps+16 ounce: 24 ounces (± 679.8g)
Anchor clamps+8 ounce+16 ounces: 32 ounces (± 906.4g)
Machine is set at the desirable sampling time, removes protective layer from test bars.
Then the rubber batten is placed in the anchor clamps, by the extrusion spring load clamps and make batten slide to certain position to measure viscosity the stainless steel strip in the last anchor clamps.
Read the reading of power from ergometer, " viscosity " numerical value that the reading of this power equals to measure.
This numerical value represents that with psi meter reading represents with ounce and contact area is represented with square inch.Test bars has following size:
Specimen width 6mm or 15mm
Length 6cm
Thickness 0.15cm
For 5 samples of each mixture test. Blend
In Banbury mixer, prepare blend, 120 ℃ of operations down, to wherein adding polymkeric substance, carbon black, softening agent, curing bag and Escorez resin.Adopt the blend working cycle of two steps,, in 30 minutes, add carbon black, oil and other additives, and have a down dip at 150 ℃ and to pour out masterbatch wherein at initial adding polymkeric substance.In ensuing 30 minutes, carry out compoundly then, add the Escorez resin during this period and solidify bag.Have a down dip at 110 ℃ at last and pour out product.
Green strength is not carry out the maximum, force (during surrender) that writes down during the Elongation test value divided by the initial horizontal section of test film to vulcanizing sheet.Employing is connected to computer and the Instron of electronics thickness piece (Instron) 4502 testers are installed measures this power.Test 5 samples, each sample is taken from mixed sheet, and this mixed sheet is aging a whole night at room temperature.
The result is as follows:
EPDM is the basic mixture of feature 100 100 100
Chloroprene rubber standard substance basis mixture (reference) 100
Escorez??5600 10 parts (100 parts umber in rubber)
Escorez??2520 10 parts (100 parts umber in rubber)
Mooney viscosity (based on ASTM D1656)
ML(1+4)@100℃，??MU ＞200 65
Green strength (Exxon testing method TS 02-10)
Maximum, force, kN/m 13.1 3.8
Toughness, Mpa 0.014 1.7
Green strength: (MPA) after the splicing 1.4 0.7 0.95 0.96
Tel-Tack，psi(kPa) 3.6(25) 2.2(15) 9.5(66) 11.8(81.4)
Based on above explanation, we require following claim.

Claims (29)

1. goods comprise a kind of multilayered structure, wherein one deck mixture of comprising ethene, alpha-olefin copolymer and/or ethylene ' alpha '-olefin diene terpolymer and containing the hydrocarbon resin of aromatics at least.
2. the goods of claim 1, wherein alpha-olefin has 3 to 25 carbon atoms.
3. claim 1 or 2 goods, wherein alpha-olefin is a propylene.
4. claim 1 or 2 goods, wherein diene comprises 5 to 15 carbon atoms.
5. the goods of claim 3, wherein diene comprises 5 to 15 carbon atoms.
6. claim 1 or 2 goods, wherein diene is a cyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene or vinyl norbornene.
7. the goods of claim 3, wherein diene is a cyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene or vinyl norbornene.
8. the goods of claim 4, wherein diene is a cyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene or vinyl norbornene.
9. the goods of claim 5, wherein diene is a cyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene or vinyl norbornene.
10. claim 1 or 2 goods, wherein terpolymer comprises 0.5 to 15wt% diene.
11. the goods of claim 1 or 2, wherein resiniferous layer comprises 1 to 25wt% resin.
12. the goods of claim 1 or 2 comprise 4 to 15wt% resin.
13. the goods of claim 1 or 2, wherein, according to vinylbenzene equivalent meter, the hydrocarbon resin that contains aromatics has 3% to 75% aromaticity.
14. the goods of claim 9, wherein resin is group aliphatic resin and the blend that contains the resin of aromatics.
15. the goods of claim 10, wherein resin all is an aromatics.
16. the goods of claim 1 or 2, it also comprises rosin ester, polyterpene or the two all has.
17. the goods of claim 1 or 2 further contain a kind of vulcanizing agent that is used for rubber.
18. by the claim 1 of coextrusion preparation or 2 goods.
19. sulfurized claim 1 or 2 goods.
20. the goods of claim 14, wherein goods are V-belts.
21. the goods of claim 15, wherein goods are V-belts.
22. the goods of claim 14, wherein goods are tires.
23. the goods of claim 15, wherein goods are tires.
24. the goods of claim 14, wherein goods are flexible pipes.
25. the goods of claim 15, wherein goods are flexible pipes.
26. the goods of claim 14, wherein goods are thin slices.
27. the goods of claim 15, wherein goods are thin slices.
28. contain the purposes that the hydrocarbon resin of aromatics is used to improve the rubber viscosity of ethylene and/or ethene, alpha-olefin diene copolymers rubber.
29. method for preparing rubber composite, wherein ethene, alpha-olefin copolymer rubber and/or ethene, alpha-olefin diene terpolymer rubber and additive and aromatic hydrocarbon resin are combined with each other, wherein rubber is at first compound with other additives that add, and adds aromatic hydrocarbon resin in the back half-life of compounding period.
CN01803679A 2000-01-13 2001-01-12 Laminar articles containing layer of ethylene containing polymer elastomers containing aromatic resins Pending CN1419592A (en)

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GBGB0000674.2A GB0000674D0 (en) 2000-01-13 2000-01-13 Laminar articles containing layers of ethylene containing polymer elastomers containing resins
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DE19734035A1 (en) * 1996-08-07 1998-02-12 Sumitomo Chemical Co Adhesive resin composition
KR20000036212A (en) * 1996-09-20 2000-06-26 엑손 케미칼 패턴츠 인코포레이티드 Metal salts of acrylic or methacrylic acid as curatives for compositions containing halogenated isomonoolefin/para-alkylstyrene copolymers
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